Dyeing vegetable fiber



Patented Sept. 7, 1937 UNITED STATES 92,429 DYEING VEGETABLE man PATENTOFFICE 1 Fritz Straub and Walter Anderau, Basel, Switzerland, assignorsto Society oi Chemical Industry Basle, Basel, Switzerland No Drawing.Application February 26, 1936, Serial N0. 65,922. In Switzerland March8, 1935 8 Claims.

invention consistsin the production of fast tints on vegetable fibers bydyeing the vege-.-

table fiber, for instance, cotton or artificial silk made fromregenerated cellulose, with a sparingly soluble or insoluble complexmetallic compound of a direct cotton dyestufl.

As direct cotton dyestuffs which in this invention are used in, the formof their sparingly soluble or insoluble complex metallic compounds,

are to be understood; for example, such disand polyazo-dyestuffs as haveaiiinity for the vegetable fiber; such dyestuffs may be constructed 0ailinity for vegetable fibers.

ponent for making the direct cotton dyestufl must be one which willensure at least one lakediazo-components are, for example, thosecontaining in ortho-position to the diazo-group a hydroxyl-, carboxyloralkoxy-group or the salicylic acid grouping. In order to obtain from thedirect cotton dyestufi the sparingly solubleor insoluble complex metalcompound by treatment with an agent yielding metal there may be usedeither an insoluble direct cotton dyestufl or a soluble dyestuff ofwhich the complex metal compounds are sparingly soluble or insoluble.

From the preceding it will be' seen that for the construction of thedirectcotton dyestuffs there are available, besides the usual aromaticamines of the benzene and naphthalene series, which may containlake-forming groups, as diazocomponents, and besides the usual phenols,naphthols and amines as couplingcomponents, in particular direct dyeingcomponents, for example matic or aromatic series, which may also containstilbene, derivatives or ureas from ,arylene diamines; also acetoaceticacid arylides, aminonaphthols and their sulfonic acids and the like.

In producing the complex metallic compounds serving as parent materialfor the invention and which may contain two or'more metals, such ascomponents of chromium, iron, cobalt, nickel, aluminium, manganese,zinc, vanadium, titanium and especially copper, the direct cottondyestuffs or mixtures of such dyestufl's may be treated with the agentyielding metal in acid, neutral or alkaline medium in a finely dividedstate, either under pressure or not, and in presence or absence ofadditions, for instance salts of organic or inorganic acids, or freeacids, for example sodium formate, benzenesulfonic acid,naphthalenesulionic acids, sodium acetate, common salt, Glauber's salt,formic acid, acetic acid or tartaric acid.

Vegetable fibers may be dyed with the sparingly soluble or insolublecomplex metallic compounds of direct cotton dyestufls in the mannerusual for dyeing with direct cotton dyestufis, for example by means ofbaths containing the dyestufi and Glaubers salt and, advantageously,alkali carbonate, such as sodium carbonate. It is advantageous to usethe dyestufi in the most finely subdivided or highly dispersed form; forinstance the form obtained by grinding the dyestufi as powder or as apaste containing fluid material, for example an aqueous paste, in theusual apparatus, such as a ball mill or a roller mill, or by windsifting. In many cases it has been found advisable to dye with thedyestufl in presence of a dispersing agent, a wetting agent oremulsifying agent, that is to say in presence of capillary active anionsor cathions or capillary active substances which'are not ionized. Suchmaterials are, in example, organic derivatives of ammonia, for exampleamines of the aliphatic, hydroarohydroxyl-groups or other substituents(for example pyridine, amines, alkylamines, methanolamines,ethanolamines, cyclohexylethanolamines, butylethanolamines), sulfonicacids of the hen-- zone or naphthalene series, which 'contain alkylganiccompounds of high molecular weight, for

example polymerization products from aldehydes and soluble degradationproducts of cellulose.

In many cases good dyeing results are particularly obtained when thefinely dispersed dyestuff is boiled with water for some time in theso-called dissolving vat or when'the finely dispersed dyestufl is addeddirectly to the boiling Ezqmple 1 10 parts of the copper compound of thedyestuif of the formula:

dye-bath, which may contain the usual additions, such as Glauber's saltand sodium carbonate at the beginning of the dyeing; the duration ofdyeing can be somewhat longer than that usual, that is to say about 1-2hours.

That form of the invention has proved very satisfactory in which dyeingis conducted in the presence of ammonia or an organic derivative ofammonia; of these the aliphatic amines and particularly those whichcontain hydroxyl-groups, such as the alkylolamines (for instance mono-,dior triethanolamine or mixtures of these bodies) give good results.Instead of adding these amines and these dyestufis or the mixture ofthese amines with these dyestuffs, obtainable by grinding the amine withthe dyestuff, to the dye-bath, the procedure may be such that theproduct formed from the agent yielding metal, the amine and the dyestuffmay be so added. Such products may be' made, for instance, by treatingthe dyestuif with the agent yielding metal in presence of the amine orby the action of the amine on the metalliferous dyestufl, water presentin the reaction mixture being distilled, if desired. These products areof the consistency of thick liquids; they are soluble in water and inconsequence of this property are well suited for the present invention,in which the amine is at least partially decomposed by hydrolysis in thedyeing process.

OH: (L-OEI the Ross 00H m a are heated in the form of an aqueous pastewith 20 parts of commercial triethanolamine while stirring on theboiling waterbath until the dyestufi has dissolved. A part of the wateris then evaporated and. there is obtained a yellow viscid mass whichdissolves clearly in water.

The dye-bath is prepared, consisting of 2000 parts of water at 30-40 C.,2 parts of calcined sodium carbonate and 2.5 parts of the solution ofthe dyestufi obtained as described above; 100 parts of cotton areentered and the bath is heated in-the course of haliF-an-hour to 90-100C. 30 parts of crystallized sodium sulfate are added and dyeing iscontinued at the same temperature for 30-40 minutes. The goods are thenrinsed and soaped in another bath containing per litre 5 parts ofMarseilles soap for half-an-hour at 50 C. Rinsing and drying follow.

The cotton is dyed yellow tints of very good fastness, particularly towashing. When the dyed goods are washed for half-an-hour in a bath at-90" C. containing, perlitre, 2 parts of calcined sodium carbonate and 5parts of Marseilles soap, together with white cotton, the latter remainsuncoloured.

Instead of triethanolamine there may also be used ethylene-dlamine orpolyalkylenediamines. When there is used for the dyeing a dyestuilsolution obtained by treating the copper compound of the azo-dyestufl.of the formula CH: (L0H N OM an;

co O OH O OH tan COOH with triethanolamine there is obtained a brownorange tint which also has good fastness to washing.

Blue-violet tints fast to washing are obtained when the dyestuif used isobtained by the action of triethanolamine' on the copper compound of.the dyestui'f of the formula com copper compound of the dyestuii of theformula I aoaaaaa m I 3 In a similar manner to that described in thesecond paragraph of this example artificial silk rims Q soul I v OCH; Nu7 00m I 3091a QM N: QM OH 0011 on, n n cm coon a blue dyeing fast towashing is obtained, and

from the product of the action of triethanolamine on the copper compoundof the dyestufl of the made from regenerated cellulose can dyed but thetemperature of the dyeing operation should be about 75-80 C.

formula I I no,s I I soar I I OCH; NH 0cm no? Gum: N= AON=NQOH I ooH on.I H H I211; oon

there is also obtained a blue dyeing fast to wash- Example 2 7 ing; fromthe product of the action of triethanolamine on the copper compound ofthe dyestuif of A boiling dye-bath is prepared consisting of the formula2000 parts of water, 2 parts of calcined sodium I 0on NH I 0cm H0-QN=Qxhn I (ID-rang :nOon

0011 H; e H OH on, (30011 a blue dyeing fast to washing is obtained;from carbonate. and 0.25 part of the finely ground the product of theaction of t'riethanolamine on paste of the copper compound of thedyestuif of the copper compound of the dyestufi of the the formula IHols soiu ocn. NH I 0on1 HOQ-N: Quitv w-Nat N=N--0n H 00H CH1 H n on. I$0011 formula I V v v I 100 parts of cotton are entered and boiling isH0;S soin OCH:

a greenish-grey dyeing is obtained, and from the product of the actionof triethanol amine on the copper compound of the dyestufl of theformula a blue grey fast dyeing is obtained.

continued for about 1% hours. The goods are then rinsed and soaped inanother bath containing per litre 5 parts of Marseilles soap for half-Hois OCH;

SOIH- an-hour at 50 C. Rinsing and dyeing follow.

I I NH-C o-1-m I OCH: I

on; I H on ocm '0 on can. I NH-C O'-N I HO-QN= N=N N= -N=NQOH 7 00K H vv H 00H OHQMPQ-n O OH CH! The cotton is dyed blue tints fast to washing.

In like manner the copper compounds of the dyestuffs named in Example 1may be used.

A similar result is obtained if 30 parts of crystallized Glaubers saltare added to the dye-bath after it has been boiling for 1 hour.

The result in respect of the uniformity of the tints obtained isfavourably influenced when the dye-bath receives an addition of 2-5parts of sulfite cellulose waste liquor.

Example 3 A dye-bath is prepared from 2000 parts of boiling water, 2parts of calcined sodium carbonate, 1 parts of Marseilles soap and 2parts of the OCR 0011 very finely subdivided copper compound of thedyestufi of the formula COOH CH: H

100 parts of cotton are entered and are handled for 1-1 hours, whereupon30 parts of crystallized Glaubers salt are added and dyeing is continuedfor half-an-hour at boiling temperature. The goods are then rinsed andsoaped in a bath containing per litre grams of soap at 50 C. Rinsing anddrying follow. The dyeings obtained are excellently fast to washing.

Similar results are produced when the dyestufl is boiled in thedissolving vat together with the sodium carbonate and the soap and thenadded to the boiling dye-bath. Good results are also obtained bytreating the finely subdivided dyestufi in the'form of paste or powderin a dispersing mill before it is used for dyeing.

If, in the dye-bath prescribed above, there is substituted for theMarseilles soap 1 part of Turkey red oil or 2 parts of sulfite cellulosewaste liquor or 1 part of sodium l-lso-propyl-naphtha- SOaH . BOZH oornm: I I

con m n n on,

Example 4 A dye-bath is prepared consisting of 2500-3000 parts of water,a. solution of the copper compound of the dyestufl of the formula :8 EI) H my I .per liter 5 grams of Marseilles soap for ,5 hour at 50 C.,rinsed again and dried. The cotton is dyed greenish-blue tints of verygood fastness to washing.

Example 5 2.5 parts of the azo-dyestuif of the formula are convertedinto the copper compound by treatment with copper sulfate. The insolubleprecipi- SOxH -CH: OOH

tate is filtered, pressed and treated in the form of a moist paste with7 .5 parts of triethanolamine on the water-bath until a syrupy massclearly soluble in water has been formed, whereupon the water isdistilled off. There are obtained 10 parts of the complex coppercompound of the azo-dyestuff which has been rendered soluble and whichis dissolved in 3000 parts of water. 100 parts of boiled jute yarn areentered into this solution, mixed with 40 parts of Glaubers salt anddyed for 1 hour while boiling. v

The jute yarn is dyed yellow fast to light and water.

Instead of jute yarn, wood bast and straw-plaiting may be dyed inanalogous manner.

tints which are Example 6 10 parts of the copper compound of OH: COOHare dissolved with 40 parts of triethanolamine in 500 parts of hotwater. The clear solution is added to a paper mass containing 1000 partsof cellulose. The whole is mixed for sometime whereby the cellulose isstrongly dyed by the dyestufl. 60 parts of aluminium sulfate and 40parts of resin glue are then added to the mixture and worked up in themanner usual for 0 CIHI H can} 0 0 OH paper. There is obtained agrey-blue colored paper of excellent tastness to water and light.

I Example 7 m 10 parts of the azo-dyestufl of the formula SOiH OCH:

are dissolved in 500 parts 01' water and mixed at 70-80 C. with asolution of 6 parts of thecopper salt of glycollic acid in warm water.The whole is stirred for sometime at TO-80 C. For dyeing there may beused either the solution of the amdye'stufi containing copper andglyeocollic acid complexly bound which has formed, or the new nos N=NN=N COOH CH: H

complex compound can be separated by means of common salt and dried. Thecomplex copper compound which has separated remains watersoluble alsoafter drying, whereas by treating with the usual Vcoppering agents;-suchas copper I sulfate, copper acetate, ammoniacal copper oxide,

sparingly soluble to insoluble complex copper compounds are obtained.

A paper mass containing 1000 parts of solid cellulose mass is dyed withthe solution of the copper complex of the dyestufi obtained in thepreceding paragraph, by treating the paper mass with the dyestuffsolution for some time in theshaking machine or the rolling mill. Thecomplex copper compound of the dyestufi is SOaH OCH:

I NH I 0011. HOQN= -Q-N=N N=N N=NQ-OH A 00H I on} 'H a on. con

with 2 parts of the sodium salt of the sulfonated Example 8 3 parts ofthe dyestufl obtainable by condensing 1 mole ofdinitrostilbene-disulfonic acid with 2 moles of the .azo-dyestuflf fromdiazotized 1- amino-4-hydroxybenzene-3-carboxylic acid and1:3-phenylenediamine in the presence of caustic soda solution accordingto the process of U. S. Patent 1,861,323, are boiled with 1.5-part oithe copper salt of glycocollic acid in 100 parts of water, and thesolution thus obtained is diluted with water to 3000 parts by volume.100 parts of jute yarn are introduced into the dyeing liquor and afteraddition of 40 parts of Glaubers salt the material is dyed for 1 hour at95 C. Therevis obtained a brown dyeing of very good ta'stness to water.

SOaH I 0cm Coconut fiber can be dyed in analogous manner. 1

Example 9 2 parts of the copper compound of the 'azo-dyestuff of theformula NH I OH:

I H on, con

are ground in a ball mill with parts of the sodium salt of thesulfonated condensation prodnot from benzylchloride and naphthaleneuntil a,

which 100 parts of cotton are introduced at 30-,

40 C. The temperature of the bath is raised to boiling in the course ofhour, whereupon 30 parts of Glaubers salt are added and dyeing iscontinued for 1 hour at 95-100 C. The cotton is then washed and dried.There are obtained blue tints of very good fastness to light andwashing.

Similar results are obtained when dyeing with a mixture which has beenobtained by grinding together 2 parts of the copper compound of thedyestufl? of the formula SOIH condensation product from benzylchlorideand naphthalene.

Greenish-blue dyeings of good tastness to light and washing areobtained.

A yellowdyeing of very good rastness to washing and light is obtained bya similar method of working when using the copper compound of thedyestufl! Example 1o- OOH Hz in the form of an aqueous paste containing20 per cent. of dyestuif are suspended in 200 parts of water, mixed with10 parts of an emulsifying agent consisting of glue andsoap, heated fora long time to 40 to 60 0., and vigorously stirred. This treatment mayalso be carried out for a shorter or longertime at higher temperatures,for example at -100 C. The mixture thus obtained is used either directlyfor dyeing, or it may be partly or completely evaporated in a vacuum andthen ground.

For dyeing there is prepared a bath having a temperature of 30-40 C. andcontaining per 100 parts of cotton 2 parts of calcined sodium carbonateand 2 parts of the above mentioned aqueous paste. The cotton isintroduced and the bath is heated to boiling temperature within /2 hour,whereupon 30 parts of Glaubers salt are added and dyeing is continuedfor a further hour at -100 C. 'After washing and drying there'areobtained blue tints of very good fastness to light and washing.

If instead of the emulsifying agent mentioned 0 in this example there isused a pyridine solution of castor oil sulfonate similar results areobtained.

Example 11 10 parts of the dyestuif of the formula are converted intothe complex copper compound with copper sulfate in usual manner. Thewater-insoluble copper compound is filtered, washed and pressed. Thepressed material is made up into a paste of 50 parts by weight by meansof water, mixed with 10 parts of the sulfonated condensation productfrom stearic acid and orthophenylenediamine, and vigorously stirred fora long time, until a homogeneous mass has been formed. A dye-bath is nowprepared consisting of 2000 parts of water, 2 parts of sodium carbonateand 6 parts of the above named mixture, into which parts. of cotton areintroduced at 30-40 C. The temperature is raised. to boiling in thecourse of 5 hour, whereupon 30 parts of Glaubers salt are added anddyeing is continued for 1 hour at 95-100 C. The cotton is then washedand dried. There are obtained yellow tints of very good fastness tolight and washing.

Similar results are obtained when using under otherwise unchangedconditions instead of the sulfonated condensation product from stearicacid and ortho-phenylenediamine an emulsifying agent consisting of glueand soap or sodium isopropylnaphthalenesulfonate.

I OH:

H OH| OOH Example 12 The dyestufl of Example 9 of U. 8. Patent1,861,323, pa e 3, lines 102-106, obtained by condensation ofdinitrostilbene-disulfonic acid with the azo-dyestufl from diazotizedl-acetylaminolater use.

A dye-bath is prepared, consisting of 2000 parts of water, 2 parts ofcalcined sodium carbonate,

and 2 parts of the dispersed dyestufl; 100 parts of cotton are enteredat 3040 0., and the bath is heated to boiling in the course of hour,whereupon 30 parts of Glaubers salt are added and dyeing is continuedfor a further hour at 95-100 C. The cotton is then washed and dried.

There are obtained orange tints of very good fastness to light andwashing.

Example 13 The dyestuff of the formula Hols 803K I! on NH on =N N=N n onNO:

is converted in an aqueous solution into the very dimcultly solublecopper compound by treating it in the usual manner with agents yieldingcopper. After filtering and washing the copper compound is dried andground in a ball mill or roller mill with equal parts of the sodium saltof the diamylsulfophthalic acid ester.

2 parts of the dyestuff mixture thus obtained are boiled in about 10litres of water and added to a dye-bath at 30-40 .C. and containing1500- 2000 parts of water as well as 2 parts of calcined sodiumcarbonate. 100 parts of cotton are entered and the temperature of thebath is raised to boiling in the course of hour, whereupon temperatureis maintained between 95-l00 C. for

ness to light and washing.

Example 14 The dyestufi of the formula parts of crystallized nickelsulfate in aqueous solution. The separated water-insoluble precipitateis filtered. Into a dye-bath consisting oi! 1500 parts of water, 2 partsof calcined sodium carbonate, 30 parts of Glaubers salt, 2 parts of thesodium salt of the diamylsulfophthalic acid ester and the complex nickelcompound produced above, are introduced 100 parts of cotton at- 30-40C.; the temperature of the bath is raised to boiling in the course of Ahour and maintained for about %-1 hour, whereupon the material isemulsifying agent consisting of glue and soap.

, Example 15 The dyestuff of the formula is converted into thecomplex-cobalt compound by mixing for example 2 parts of thisazo-dyestuff, dissolved in 100 parts of water, at 80100 C. with anaqueous solution of 1.5 parts or cobalt chloride, stirring for some timeand filtering the waterinso'luble cobalt compound of the dyestuif whichhas separated; For dyeing 100 parts of cotton 2 parts of the complexcobalt compound are added to a dye-bath consisting of 1500 parts ofwater, 2 parts of the sodium salt of the diamylsulfophthalic acid ester,2 parts of calcined sodium carbonate and '30 parts of Glaubers salt. Thematerial is introduced at 30-40 C., the temperature of the bath israised to boiling within /2 hour and maintained for about 1 hour,whereupon the cotton is washed and dried.

There are obtained brown-violet tints of veryole 4 r OCH: NH

' OOH CH: H e 1 H 7 good fastness to, washing and light which may stillbe improved by soaping in another bath containing per liter 0.5 gram, ofMarseilles soap at 40 C.

Instead of the sodium salt of the diamylsulfophthalic acid-ester theremay also be usedthe on I NH I oiN H n i 0011 same quantity of anemulsifying agent consisting of a mixture of. glue and soap, or thecorresponding quantity of the sodium salt of the sultonated condensationproduct .from. benzylchloride and naphthalene.

Example 16 The dyestuff obtained by condensation of 1 mole ofdinitrostilbene sulfonic acid with 2 moles of the azo dyestuif fromdiazotized 1-amino-4- hydroxybenzene-3-carboxylic' acid and1.3-phenylenedlamine, in the presence of caustic soda solution accordingto the process of U. S. Patent 1,861,323, is converted in an aqueoussolution into' the water-insoluble complex copper com pound'by treatmentin the usual manner with agents yielding copper. The copper compound isseparated, washed, dried and extremely finely ground. v

2 parts of this cupriferous dyestufi are ground with 1 part of thesodium salt of glycocollic acid,

whereby there is obtained a water-soluble form of thecomplex copper.compound which is suitable for dyeing cotton from a neutral orsodaalkaline Glaubers-salt bath.

2 parts of the ground material are boiled with about 100 parts of waterand added to a dyebath containing 1500-2000 parts of water and 2 partsof calcined sodium carbonate at 30-40 C. 100 parts of cotton areintroduced into this bath and the temperature is raised to boiling inthe course of ii -V hour, whereupon 30 parts of Glaubers salt are addedand the temperature is maintained for 1 hour between 95-.-100 C. Thecotton is then rinsed and dried. There are obtained brown tints of goodfastness to'light and washing. v

. Example 17 I 1 part of the dyestufl of the formula 4 80:11 I OCH:

(sodium salt) is ground in a. mill with 0.5 part oi. the copper salt ofglycocollic acid and 0.5 part of the nickel salt of glycocollic acid.The ground material is used for dyeing 100 parts of cotton by dissolvingit in 1500 parts of water, 2 parts of calcined sodium carbonate, anddyeing the cotton for 1 hour at 90-l00 C. Washing and drying follow.There are obtained blue tints of good iastness to washing and light.Before drying the dyeing may be soaped for about hour in another bathcontaining per cent or soap, whereby the fastness to washing isimproved.

Example 18 The dyestufi' of the iorumla OOH H OH is converted into thecomplex nickel-cobalt compound by mixing 1 part of the dyestui'i! inaqueous solution with the solutions of 0.28 part of crystallized nickelsulfate and 0.28 part of cobait sulfate, stirring the whole in the heatand filtering the precipitate. To the paste of the complex metalcompound thus obtained there is added 1 part of a mixture consisting ofequal parts of Marseilles soap and glue, the whole is homogeneouslymixed and evaporated to dryness in a vacuum. The dried material is thenfinely ground.

A dye-bath is prepared consisting of 1000-1500 parts of water, 2 partsof calcined sodium carbonate and 30 parts of Glaubers salt. 100 parts ofcotton are dyed by introducing the material at 30-40 C.. heating thebath to boiling in the course of 20-30 minutes, maintaining thistemperature for about 1 hour, washing and drying. The dyeing thusobtained has good fastness to washing and light.

Example 19 v 1 part of the dyestufi of the formula OHIO ' ing and dryingfollow. There are obtained bluegrey tints of good iastness to washingandlight.

What we claim is: 1

1. Process for the production oi fast tints on vegetable fiber,comprising dyeing the vegetable fiber with finely subdivided complexmetal compounds of direct azo-dyestuils for cotton, said compounds beingsparingly soluble to insoluble in water and in dilute alkalies.

2. Process for the Production of fast tints on vegetable fiber,comprising dyeing the vegetable fiber with finely subdivided complexcopper compounds of direct azo-dyestuilfs for cotton, said compoundsbeing sparingly soluble to insoluble in water and in dilute alkalies.

3. Process for the production oi fast tints on vegetable fiber,comprising dyeing the vegetable fiber with complex copper compounds ofdirect azo-dyestufis for cotton, said compounds being sparingly solubleto insoluble in water and in sosn dilute alkalies, in presence ofcompounds selected from the group consisting of dispersing, wetting andemulsifying agents.

4. Process for the production of fast tints on vegetable fiber,comprising dyeing the vegetable fiber with complex copper compounds ofdirect azo-dyestufls for cotton, said compounds being sparingly solubleto insoluble in water and in dilute alkalies, in presence of organicammonium bases.

5. Process for the production 01' fast tints on vegetable fiber,comprising dyeing the vegetable fiber with complex copper compounds ofdirect azo-dyestufis for cotton, said compounds being sparingly solubleto insoluble in water and in dilute alkalies, in presence of aliphaticamines.

6. Process for the production 01' fast tints on vegetable fiber.comprising dyeing the vegetable fiber with complex copper compounds ofdirect azo-dyestufis for cotton, said compounds being sparingly solubleto insoluble in water and in dilute alkalies, in presence of aliphaticamines containing hydroxyl groups.

7. Process for the production of fast tints on I CH:

N=N N=NQOH a on. 0 on vegetable fiber, comprising dyeing the vegetablefiber with finely subdivided complex copper compounds of directazo-dyestufls for cotton, said compounds being sparingly soluble toinsoluble in water and in dilute alkalies, and soaping the dyeing thusobtained.

8. Process for the production of fast tints on vegetable fiber,comprising dyeing the vegetable fiber with complex copper compounds ofdirect azo-dyestuils for cotton, said compounds being sparingly solubleto insoluble in water and in dilute alkalies, in'presence of aliphaticamines containing hydroxyl groups, and soaping the dveings thusobtained.

' FRI'I'Z B'I'RAUB.

WALTER. ANDERAU.

